Insecticidal compositions



Patented Nov. 14, 1944 umrEosTAT Es PATE F CE..-

INSECTICIDAL COMPOSITIONS Kenneth E. Max well, Martinez, cam, asslgnor to Shell- Development Company, San Francisco,

Calif., a corporation of Delaware No Drawing. Application January 12, 1943,

7 Serial No. 472,141

13 Claims.

The effect of my depositing agents for solid insecticides in aqueous suspensions may be explained on the basis of electroklnetic phenomena. Aqueous suspensions of solvent insecticides,

fruits, or growing trees. Thus lead arsenate,

carry-off of the insecticide and increasing the deposition thereof from an aqueous carrier that the instant invention is directed. It will be obvious that with increased deposition of the insecticide savings thereof will be effected and a lower concentration of insecticide in water will be required to obtain a lethal dosage.

as well as wet-leaf surfaces, normallyqpossess negative electrostatic charges. Thus when sprayed onleaves such materials tend to be repelled by the leaf surfaces. The magnitude of the negative charge is directly related totheability of the insecticide 'to attach itself to the leaf and consequently the conventional aqueous suspension of a solvent insecticide does not readily deposit, on the material sprayed. In keeping therewith, Ibelieve the eflectiveness of my depositing agents to be due to a reduction in the negative charge or the establishment of a straight positive charge on the suspended particles and consequently a lowering of the repelling tendency or an increase in the attraction of the ob- Ject sprayed for the insecticide.

The compounds suitable for my purpose are the salts of low molecular weight carboxylic acids, preferably polycarboxylic acids and especially -hydroxy substituted dicarboxylic acids, with the A further objectis to provide a depositing agent which will cause the insecticide to adhere firmly to the fruit or foliage.

The term "insecticide or "solid insecticide as used herein will refer to such substances as Bordeaux mixture, copper sulfate, cryolite, lead arsenate, red copper oxide, sulfur, either with or without the addition of the additives known to be used therewith, such as toxicants, spreaders, etc. Such .toxicants may comprise pyrethrum, rotenone, derris resins, nicotine, aliphatic thiccyanates, dinltro cresols, dinitro phenols, ketones, ketols, halogenated hydrocarbons such as chlorinated napthalenes, cresylic acid, alkyl amines, pine oils,-roslnols, etc.

I have discovered that when suitable salts of carboxyllc acids with certain amides of polyamines with fatty acids are added to an aqueous carrying medium containing a solid insecticide in suspension and this mixture sprayed on fruit and foliage a smooth and uniform deposit of unusual magnitude of the insecticide is obtained. The invention will be more thoroughly understood from the following description:

higher fatty acid mono-amides of alkylene polyamines.

The low molecular weight acids which may be used to form salts are preferably aliphatic polycarboxylic acids having less than 7 carbon atoms, and especially those acids in which the ratio of carbon atoms to carboxyl groups is less than 5. Such acids as oxalic, malonic, succinic, maleic, fumaric, glutaric, glutaconic, adipic, allylmalonic acids and the like may be used. Especially eflective are the hydroxy substituted polycarboxylic acids, such as tartronic, malic, dihvdroxysuccinic, trihydroxyglutaric and citric acids.

The amides are preferably obtained .by reaction of alkylgne polyamines with higher molecular weight hydrocarbon carboxyllc acids which may contain substitution radicals, such as Cl, OH, etc. These higher acids preferably contain at least 10 carbon atoms, and in general not more than 30 carbon atoms. These higher acids may be aliphatic, naphthenic, or aromatic carboxylic acids, which have a terminal hydrocarbon chain of at least 8 carbon atoms, which terminal chain is unsubstituted with polar radicals. For examle, suitable acids include undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, melisslc acid, ricinostearolic acid, ricinoleyl lactic acid, chloracetylstearic acid, chlorinated oleic acid, linolelc acid, linolenic acid, stearyl cyclohexanoic acid, lauryl cyclopentanoic acid, decyl benzoic acid, cetyl toluicacid. cetyl phenylethanoic acid, margaryl naphthoic acid. mixtures of any two or more of the above-mentioned acids or other acids, mixed higher fattyacids derived from animal or vege- Exmnn The enectiveness of the depositing agents was determined under conditions simulating field practice. Insecticides to be treated, both with table sources for example, cocoanut oil, rape- .5 I

and without the herein described depositing seed sesame palm kernel Dam agents, were emulsified in water in a small fieldolive oil, soyabean oil. peanut oil, castor oil, seal type spray machine, capable of o-pemm I 0115' sardine and other fish 011s teaseed spraying pressures up to 1000 lbs. Numerical. W or hydrogenated animal or evaluation of the spray deposits for the variousvegetable as insecticides and additives tested was obtained and alpha-hydroxy carboiwlic aliphatic acids. by spraying weighed tomuounce on mp1 8 mi ag gggg gfigg g'g gg g wg fi bottles, the sides of which had been coated with suitable alkylene polmmines which may a thin layer of beeswax. The bottles were weighed mm th be H d m h id to the nearest milligram on an analytical bala. headrests: mass em W we we invention mcmde alkylene diamines in which and allowing sumcient time to elapse so that all the amine groups may be both primary water from the spray had evaporated. The dry and/or secondary carbon atoms and are joined was texpeditfed g the :3 m g i g g short a fif t h z gain p lz b st le averagi: :l:s: to 1 5? s: which at le s ig of iiie gnfi i i o ggo ups cm., and since they were sprayed in sets of three for each test the following equation can be mary, For example, suitable polyamines include i the diamines, such as ethylene diamine, monoder Y methyl ethylene diamine, 1-1 dimethyl ethylene 2 diamine, propylene diamine, butylene diamine, 150X3 z gigf fig m i z gii iggi xgafigg where D is the average deposit in micrograms per square centimeter and W is the total spray dime isopmpyl N'butylene dlamme and pref' residue on the three bottles in milligrams e -b yd o 2 7 -a kylene diamines, su The depositin agents tested as shown the as hydmxyethyl ethylene hydmxy table below were tested under the following conpyl propylene diamine, as well as other polymuons, amines, for example, monoethyl diethylene triamine, tetra (hydroxyethyl) tetraethylene pen- Pressure in the spray machine, lbs./sq.in. 500 tamine, di (hydroxyethyl) diethylenetriamine, Circulation time in seconds of the insectietc. cidal composition in the spraym'achine..- 30 The preferred depositing agents of the present Spray nozzle orifice diameter.. 5inches %4 invention are prepared by initially reacting an Exposure of sample bottles to spray alkanol alkylene diamine, for-example, ethanol seconds 6 N-ethylene diamine, with a higher aliphatic car- 40 Distance spray nozzle to the sample bottle boxylic acid, for example, a mixture of palmitic f 6 Tana:

sample 0 id p Dep Deposit s0 no a N Solid insecticide gglgf Depositing agent Bat/m0 881m (gigs/m) m -figs l Ieedorsenata(brandA)-- 3 N 20 .1.00 i 2 3 The malate 01- f 0 I mwtmmk-mnomn-on 0.25 as 1.80 3 d0 3 -d0 1.0 51 2.50 a"; --do a do 2.0 40 2.00 5-- Lead arsenate (brand 3).... 3 None 22 1.00 0. d 3 (Sameasin sample 2) 0.1 40 I L80 7 a a -do 0.25 41 an $35611? 1% P33 (1 3 sem'ii'sdfii'pi'zii "6. 58 3:60 12 2 an? 23 it'd 13 (in a sem''fisni'pibiliililll. "035' 3 as 1140 14. Basi eoppersulphate 6 N 40 1.00 15 in A 6 (SameasinSample 2) 0.10 62 1.20 in an e do 0.25 71 1.40 17 m 6 .do 0 0.60 1.20

The above-described specific carboxylic acid salt of hydroxy diamine is merely illustrative of compounds useful for my purpose. It will be understood that compounds meeting the tests described herein as to operativeness, for my purpose and equivalents are included within the scope of the invention.

While I have advanced certain theories of operation for my newly invented depositing agents for insecticidal materials, it will be understood that I do not limit myself to any such theory of operation set out, but only to the invention as set out in the appended claims.

I claim as my invention:

1. An aqueous insecticidal composition comprising dispersed in water a solid insecticidal toxicant and a small amount for the salt of a polycarboxylic acid of less than 7 carbon atoms with a mono-amide formed by reaction between a higher molecular weight hydrocarbon carboxylic acid and a hydroxy alkyl N-alkylene diamine.

2. An aqueous insecticidal composition comprising dispersed in water a solid insecticidal toxicant and a small amount of the salt of a polycarboxylic acid of less than 7 carbon atoms with a mono-amide formed by reaction of a carboxylic acid of a hydrocarbon having a terminal hydrocarbon chain of at least 8 carbon atoms and an alkylene polyamine.

atoms with a mono-amide formed by reaction of a carboxylic acid of a higher molecular weight hydrocarbon and an alkylene polyamine.

5. An aqueous insecticidal composition comprising dispersed in water a solid insecticidal toxicant and a small amount of the salt of a polycarboxylic acid of less than 7 carbon atoms with a monoamide formed by reaction between a higher molecular weight hydrocarbon carboxylic acid and an alkyl N-alkylene diamine.

6. An aqueous insecticidal composition comprising dispersed in water a solid insecticidal toxicant and a small amount of the salt of a dicarboxylic acid of less than 7 carbon atoms with a monoamide formed by reaction between a carboxylic acid of a higher molecular weight hydrocarbon and an alkylene polyamine, in which at.

least one of the amino groups of the polyamine is primary.

7. An aqueous insecticidal composition comprising dispersed in water a solid insecticidal toxicant and a small amount of the salt of an allphatic dicarboxylic acid of less than 7 carbon atoms with a mono-amide formed by reaction of an aliphatic hydrocarbon carboxylic acid having from 10 to 30 carbon atoms and a hydroxy alkyl N-alkylene diamine.

8. An aqueous insecticidal composition comprising dispersed in water a solid insecticidal toxicant and a small amount of the malate of the reaction product of higher fatty acids with hydroxy ethyl N-ethylene diamine.

9. An aqueous insecticidal composition comprising dispersed in water a solid insecticidal toxicant and a small amount of the malate of the reaction product of a mixture of higher fatty acids having a terminal hydrocarbon chain of at least 8 carbon atoms with ethanol N-ethylene diamine.

10. An aqueous insecticidal composition comprising dispersed in water a solid insecticidal toxicant and a small amount of the malate of wherein R. represents a mixture of acyl radicals from palmitic and stearic acids.

11. A method for increasing the deposition of suspended insecticidal toxicants from an aqueous carrier. comprising adding thereto a small amount of the salt of a polycarboxylic acid of less than 7 carbon atoms with an acylated alkylene polyamine, in which the acyl radical has a terminal hydrocarbon chain of at least 8 carbon atoms.

12. A method for increasing the deposition of suspended insecticidal toxicants from an aqueous carrier, comprising adding thereto a small amount of the'salt of a polycarboxylic acid of less than 7 carbon atoms with an acylated alkanol N-alkylene polyamine, in which the acyl radical has a terminal hydrocarbon chain of at least 8 carbon atoms.

13. A method for increasing the deposition of suspended insecticidal toxicants from an aqueous carrier, comprising adding thereto a small amount of the malate of wherein R represents a mixture of acyl radicals irom palmitic and stearic acids.

KENNETHE. MAXWELL. 

